Copper-based Graphene Nanoplatelet Composites as

Interconnect for Power Electronics Pacakging

Jing Wang Zhaoxia Zhou Wen-Feng Lin
Wolfson School of Mechanical, Electrical, Loughborough Materials Department of Chemical Engineering
Manufacutring Engineering Characterisation Centre (LMCC) Loughborough University
Loughborough University Department of Materials Loughborough, UK
Loughborough, UK Loughborough University W.Lin@lboro.ac.uk
J.Wang6@lboro.ac.uk Loughborough, UK
Z.Zhou@lboro.ac.uk
Changqing Liu* Lee Empringham
Wolfson School of Mechanical, Electrical, Behzad Ahmadi School of Electrical and Electronic
Manufacutring Engineering School of Electrical and Electronic Engineering
Loughborough University Engineering University of Nottingham
Loughborough, UK University of Nottingham Nottingham, UK
* Corresponding author: Nottingham, UK Lee.Empringham@nottingham.ac.uk
C.Liu@lboro.ac.uk Behzad.Ahmadi@nottingham.ac.uk

Abstract—The present investigation demonstrates a single-
step electrodeposition route for the fabrication of compact
copper-based graphene nanoplatelets (GnPs) nanocomposite
coatings, with dispersed GnP co-deposition. The effect of cathodic
current density on the surface morphology of the deposits was
examined. With increasing deposition current densities from 10
to 40 mA/cm2, there seemed to be a gradual increase in the lateral
size of co-deposited GnPs and a decrease in their distribution
density, along with a progressive decrease in the deposit surface
feature. The chemical state of GnP from the sub-surface region of
composite coatings was assessed using XPS in conjunction with
Ar ion sputtering and found comparable to that of pristine GnPs.
The Cu-GnP composite coatings exhibited slightly higher
electrical sheet resistance, compared to that of the untreated Cu
and pure Cu deposited counterparts.
Keywords— power electronic systems packaging, heterogeneous
integration, composite electrodeposition, Cu electroplating
I. INTRODUCTION
Hetergeneous integration, which addresses integrating
different components and functionalities into a single, multi-
featured package or functional block, has emerged as a
promising solution for next generation power electronics
converters. In this approach, components are used in more
optimum conditions by focusing on package layout and
interconnection between components. By integrating
functionalities such as thermal interface, filtering components,
switching devices and high current interconnects in the same
package, converters can be designed to operate at higher
switching frequency and therefore higher power densities can
be achieved. The heterogeneous integration of wide-band gap
(WBG) power electronics, nevertheless, necessitates a
paradigm shift in the selection of packaging materials and the
design of physical dispositions, as the conventional monolithic
approach becomes restrictive in thermal and electromagnetic
interference (EMI) management with ever increasing
This work is supported by UK EPSRC Underpinning Power Electronics
2017: Heterogeneous Integration (EP/R004501/1).
packaging densities and operational temperatures. For the
integration of inhomogeneous and dissimilar materials, as the
amount of ‘free-space’ is minimised, the differences in the
properties of these materials become ever increasingly
significant. In particular, the thermal expansion mismatches
between adjacent dissimilar materials (e.g. semiconductor
devices/copper metallisations, copper metallisations/ceramic
substrates) could cause excessive thermo-mechanical stresses at
different operational temperatures of the devices, leading to
various failure mechanisms, such as brittle cracking and fatigue
crack propagation of brittle materials (e.g. semiconductors, thin
insulating layers and ceramic substrate) [1], and void/porosity-
facilitated fatigue of soldered/sintered interconnects [2]. In
attempts to lower the mean thermal expansion coefficient (CTE)
of Cu (~ 17 ppm/°C) relative to ceramic-based devices and
substrates (e.g. SiC: 2.8 ppm/°C, AlN: 5.3 ppm/°C), this paper
constitutes part of a systematic study for the development of
cost-effective wet chemistry solutions to prepare CTE-
controlled interconnects based on nanocarbon (NC)-reinforced
copper matrix composite. Exfoliated graphene nanoplatelets
(xGnPs) were investigated in this work due to their excellent
intrinsic thermal and electrical conductivities, high current
carrying capabilities (i.e. ampacity) [3], peculiar negative
thermal expansion characteristics [4], large surface area as a 2D
nano-filler providing enhanced interfacial interaction to
capitalise the reinforcement effect, and low physical density.
The cupro-phobic nature and poor dispersion of nano-carbon
materials, nonetheless, have necessitated judicious designs over
their synthesis chemistry and processing conditions. Therefore,
surfactants and other additives [5, 6] need to be incorporated
into the electrolytes as such to promote universal co-deposition
of GnPs. Electrolytic deposition is selected for the synthesis of
composites due to its low processing temperature and the
capability to fine-tune the coating microstructure. This
investigation is hence set to understand the fundamental aspects
of the electrodeposition process to the development of the Cu-
GnP composite materials. This will lead to the development of
an interconnect material with sound dimensional stability and

  
 

thermomechanical fatigue resistance, without necessarily
compromising electrical and thermal performance.
II. EXPERIMETAL
A. Bath Formulation & Electrodeposition
All chemicals were utilised as received from Sigma-Aldrich
without further purification, unless specified otherwise.
Representative morphology of graphene nanoplatelets (nominal
in-plane size: 5 μm, surface area 50-80 m2/g, Sigma-Aldrich) is
presented in Fig. 1. Table I lists the bath formulations for both
GnP-free and GnP-loaded Cu electrodeposition. A
conventional, two-electrode glass cell configuration was
adopted in the present investigation. Electrodeposition was
conducted utilising pure polycrystalline copper substrates
(99.9%, 125 μm thickness, Advent Research Materials) as the
cathode, each with an exposed electrochemically active area of
2 × 2 cm2 defined by chemically inert tape (3M). The Cu
substrate pretreatments involved ultrasonic cleaning for 3 min
in acetone, pickling for 35 s in a 25% v/v/ aqueous solution of
H2SO4 (specific gravity: 1.83) at 20ºC, and rinsing with
deionised water. The anode was a larger platinised titanium
mesh electrode. Direct current galvanostatic deposition was
performed utilising a QPX 1200S DC power source (Thurlby
Thandar Instruments) at 20ºC with magnetically stirred
agitation at 300 r.p.m.. Current densities were applied with
equivalent electric charge passed at 12 C/cm2.
Fig. 1 – SEM image illustrating the representative morphology of graphene
nanoplatelets (GnPs)
TABLE I. BATH FORMULATIONS FOR PURE CU & CU-GNP
ELECTRODEPOSITION
Pure copper baseline Copper-GnP composite
COMPOUNDS
formulation (Bath I) formulation (Bath II)
CuSO4 ·5H2O 200 g/L
H2SO4 4 mL/L
Additive A 100 mL/L
Additive B 3.2 g/L
GnPs 0 0.8 g/L
B. Materials Characterisation
Field emission gun – scanning electron microscopy
(FEGSEM) and Energy dispersive X-ray spectroscopy (EDX)
characterisation were conducted utilising a Carl Zeiss Leo 1530
FEGSEM system, which is equipped with an Oxford
Instruments X-max 80 mm2 EDX detector. X-ray photoelectron
spectroscopy (XPS) analysis was performed utilising a Thermo
Scientific K-α X-ray Photoelectron Spectrometer with an Al
source. A pristine GnP precursor control sample was analysed
as such to ascertain the chemical state of carbon (C 1s) in the
deposited Cu-C specimens. Compositional depth profiling was
undertaken via argon ion beam sputtering to obtain in-depth
distribution of deposit composition and chemistry. The
sputtering raster size was set as 2 mm. The sputter rate was
estimated as 0.23 nm/s with reference to that of Ta2O5. The
electrical resistance of the electrodeposited samples (i.e. sheet
resistance, in mΩ/square) was assessed by a four-point probe
method utilising a Keithley 2440 5A Source meter.
III. RESULTS AND DISCUSSION
The effect of cathodic current density on the surface
morphology of pure copper and copper-GnP electrodeposits is
demonstrated in Fig. 2. For pure Cu obtained from Bath I, with
increasing galvanostatic current density from 10 to 40 mA/cm2
(Fig. 2a-d), the deposited surface morphology exhibited a
progressive refinement of the surface feature, decreasing from
the micron-sized down to submicron scales. This implies an
increasing tendency for new crystallite nucleation over
development of existing grains, which was imposed by
increasing overpotential upon electro-crystallisation. For Cu-
GnP derived from Bath II, a current density of 10 mA/cm2 (Fig.
2e) produced deposit surface features generally smaller than
those derived from Bath I, even at high current density of 40
mA/cm2 (Fig. 2d). These suggest GnP co-deposition tends to
inhibit electrochemical reduction of Cu2+ ions. No significant
co-deposition of 2D GnPs was observed at 10 mA/cm2.
However, as demonstrated from Fig. 2e, the deposit surface at
lower current density of 10 mA/cm2 showed distribution of
nano-sized particulates, indicative of potential co-deposition of
0D GnP debris. With increasing current density to 20, 30 and
further to 40 mA/cm2 (Fig. 2f-h), deposit surfaces possessed
predominant and dispersed distribution of 2D GnPs, which was
accompanied by deposit surface feature refinement. These
GnPs were generally found to increase in size and decrease in
distribution density with increasing current density. This
indicates, by changing the deposition current density, the
electrodeposition process exhibits a clear selectivity towards
the co-deposited nanoplatelets on their lateral sizes and
distributions, which could be exploited as a ‘sieving and
tuning’ tool to control GnP co-deposition. It is noteworthy that,
the exposed GnP structures exhibited certain curling, which
differed from that of the pristine state, as shown in Fig. 1. The
co-deposition of GnPs in the bulk structure of the deposits was
treated in the next from XPS compositional depth profiling.
The surface morphology of Cu-GnP deposits was generally
found to be compact and crack-free from low magnification
SEM observations. At higher magnifications (e.g. as shown in
Fig. 3) hemi-spherical, nodular formations, with sizes of up to a
few microns and GnPs co-deposited, were typically observed.
The presence of such nodules may be attributed to localised
elevated current densities during electrodeposition.
XPS compositional depth profiling was conducted to
understand the in-depth distribution of C in the bulk structure
of the deposits. A sampling area of 400 μm × 400 μm was
utilised to average out the fluctuations across the in-plane
compositions. As shown in Fig. 4a acquired from a Cu-GnP
sample deposited at 20 mA/cm2 from Bath II, the initial, un-
sputtered surface (sputter time: 0 sec) demonstrated a C 1s
singlet peak with the highest intensity, which can be attributed,
primarily to adventitious carbon (binding energy: ~ 284.8 eV)
from sample surface contamination, and secondarily to
potential presence of graphene nanoplatelets at the surface.
After the first level of compucentric Ar ion monomer sputter
(sputter time: 30 s), the adventitious carbon component was
largely eliminated upon removal of surface contamination,
exposing the GnP C 1s component. With increasing sputter
time beyond this level, the GnP C 1s peak maintained
throughout sputtering until the sputter analysis was terminated
at 330 s, roughly equivalent of 76 nm thick deposit material
removed off (sputter rates estimated with reference to that of
Ta2O5). Fig. 4b presents the narrow spectrum of C 1s at the
sputter time of 330 s after deconvolution, which showed sp2
carbon at 284.4 eV and sp3 carbon at 285.0 eV with a broad,
asymmetric tail towards higher binding energy. These are
comparable with those obtained from the pristine GnP
precursors utilised in the present investigation, which exhibited
sp2 carbon at 284.5 eV and sp3 carbon at 285.1 eV with similar
shake-up feature, as shown in Fig. 4c. An in-depth examination
of the distribution of GnP within the coatings’ bulk structure is
ongoing at Loughborough University.

(a) (b) (c) (d)

(e) (f) (g) (h)

Figure 2 – Secondary electron images illustrating the representative surface morphology of a-d) pure Cu electrodeposits derived from Bath I and e-h) Cu-GnP
electrodeposits from Bath II: a, e) 10 mA/cm2, b, f) 20 mA/cm2, c, g) 30 mA/cm2, d, h) 40 mA/cm2

(a) (b)

Figure 3 – Secondary electron images showing the morphology of nodular formation on Cu-GnP electrodeposits acquired from Bath II at a) 20 mA/cm2 & b) 30
mA/cm2.
 C/cm2, the sheet resistance became slightly increased
(a) (differences: ~ 1 mΩ/square) compared to that of untreated Cu
sheet substrates, presumably due to a reduction in the average
grain size of sample surface regions [7]. In the case of Cu-
graphene nanoplatelets deposited samples (as shown in Fig. 5),
the sheet resistance saw approximately 2 mΩ/square increases
compared to that of the untreated Cu and seemed to be not
Photoemission intesnity (Arbitrary units)

330 significantly affected by deposition current densities. The

300
270 increases in sheet resistance may be induced by the grain
240
210
180
refinement effect arising from GnP co-deposition and possibly
150
120 affected by the chemical state/distribution of co-deposited
90
60
30 Sputter time (Sec) GnPs as well. Such small magnitudes of reduction in the
0 electrical conductivity can be tolerated for practical
296 294 292 290 288 286 284 282 280 278 276 applications.
Binding Energy (eV)

Pure Cu deposited samples

Sheet resistance (m:/square)

30 Cu-GnP deposited samples
Untreated Cu substrates
sp2 bonding
(b) 28

26
sp3 bonding
24

22
-COO-

20

18
0 10 20 30 40

296 294 292 290 288 286 284 282 280 Cathodic current density (mA/cm2)
Binding Energy (eV)
Figure 5 – A plot showing the sheet resistance of untreated and deposited
samples as a function of bath formulation and deposition current densities
(c) sp2 bonding

296 294
Figure 4 – a) XPS compositional depth profiling of a Cu-GnP sample
electrodeposited at 20 mA/cm2 from Bath II showing the evolution of C 1s
narrow spectra with increasing Ar ion monomer sputtering time, b) the
corresponding C 1s spectrum taken at a sputter time of 330 s, c) C 1s spectrum
taken from the pristine graphene nanoplatelet precusor (control sample).
To examine the effect of GnP co-deposition on the electrical
conductivity of copper thin films, the sheet resistance of pure
Cu and Cu-GnP plated specimens was assessed and plotted in
Fig. 5. It was found that, by depositing pure Cu onto Cu
substrate from Bath I with an equivalent charge passage of 12
V. CONCLUSIONS
Direct current electrodeposition and characterisation of Cu-
GnP composite layers have been performed to examine the
sp3 bonding
fundamental aspects of the wet chemistry processing route to
-
the development of an interconnect material for power
-COO
electronics packaging. The composite coating surface generally
demonstrated universal and certain dispersed incorporation of
GnPs observed on the surface of the coatings. With increasing
deposition current densities from 10 to 40 mA/cm2, there was a
292 290 288 286 284 282 280 gradual increase in the lateral size of co-deposited GnPs and a
Binding energy (eV) decrease in their distribution density, along with a progressive
decrease in the deposit surface feature. The electrodeposition
process itself is evidenced to serve as a sieving and fine-tuning
tool to control the GnP co-deposition, as such to facilitate
microstructure and property optimisation of the composite
coatings. The chemical state of GnP from the sub-surface
region of composite coatings was assessed using XPS in
conjunction with Ar ion sputtering and found comparable to
that of pristine GnPs. The Cu-GnP composite coatings
exhibited slightly higher electrical sheet resistance, compared
to that of the untreated Cu and pure Cu deposited counterparts.
 ACKNOWLEDGMENT
The authors acknowledge use of the facilities and the
assistance of Dr. Keith Yendall and Mr. Luke Jones in the
Loughborough Materials Characterisation Centre. The authors
also thank Dr. Fulong Sun for his advices over plating bath
formulation.
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